Polyphenylene ether-polyester copolymers, precursors therefor, compositions containing said copolymers, and methods for their preparation

ABSTRACT

Compositions containing polyphenylene ether-poly(alkylene dicarboxylate) copolymers are prepared by a reaction between the two polymers and, optionally, at least one functionalizing agent therefor. The functionalizing agent may first be reacted with the polyphenylene ether and the resulting functionalized polyphenylene ether in turn reacted with a functionalized or unfunctionalized poly(alkylene dicarboxylate). Alternatively, an unfunctionalized or hydroxyalkyl-functionalized polyphenylene ether may be incorporated in a conventional polyester-forming reaction. The copolymer-containing compositions are characterized by a number of desirable properties including high impact strength and solvent resistance.

This application is a continuation of application Ser. No. 866,661,filed May 27, 1986, now abandoned.

This invention relates to novel resinous compositions with high impactresistance and solvent resistance, and precursors therefor. Moreparticularly, it relates to improved compositions comprisingpolyphenylene ethers and poly(alkylene dicarboxylates).

The polyphenylene ethers are a widely used class of thermoplasticengineering resins characterized by excellent hydrolytic stability,dimensional stability and dielectric properties. They are also resistantto high temperature conditions under many circumstances. Because of thebrittleness of many compositions containing polyphenylene ethers, theyare frequently blended with impact modifiers such as elastomers to formmolding compositions.

A disadvantage of the polyphenylene ethers which militates against theiruse for molding such items as automotive parts is their low resistanceto non-polar solvents such as gasoline. For increased solventresistance, it would be desirable to blend the polyphenylene ethers withresins which have a high degree of crystallinity and therefore arehighly resistant to solvents. Illustrative of such resins are thepoly(alkylene dicarboxylates), especially the poly(alkyleneterephthalates). However, such blends frequently undergo phaseseparation and delamination. They typically contain large, incompletelydispersed polyphenylene ether particles and no phase interaction betweenthe two resin phases. Molded parts made from such blends are typicallycharacterized by extremely low impact strength.

A principal object of the present invention, therefore, is to providepolymer compositions having a high degree of impact strength and solventresistance, and intermediates therefor.

A further object is to provide highly compatible polymer compositionscontaining polyphenylene ethers and poly(alkylene dicarboxylates), withbeneficial properties of both.

A further object is to provide resinous molding compositions suitablefor use in the fabrication of automotive parts and the like.

A still further object is to provide methods for preparing and treatingthese compositions.

Other objects will in part be obvious and will in part appearhereinafter.

The present invention is based on the discovery that it is possible toprepare compositions comprising polyphenylene ether-poly(alkylenedicarboxylate) copolymers in which the polyphenylene ether-polyesterlinkages include a wide variety of linking groups. As a general rule,these compositions have excellent tensile and impact properties andsolvent resistance.

Accordingly, one aspect of the present invention is compositionscomprising copolymers having the formula

    A--Z.sup.1 --B                                             (I)

wherein A is a polyphenylene ether moiety, B is a poly(alkylenedicarboxylate) moiety containing at least 30 alkylene dicarboxylateunits, and Z¹ is a linking group.

It is evident that the A and B moieties in formula I are derived frompolyphenylene ethers and poly(alkylene dicarboxylates), respectively.These two polymers will hereinafter sometimes be referred to as "reagentA" and "reagent B", respectively.

The polyphenylene ethers (also known as polyphenylene oxides) used asreagent A are a well known class of polymers. They are widely used inindustry, especially as engineering plastics in applications requiringtoughness and heat resistance. Since their discovery, they have givenrise to numerous variations and modifications all of which areapplicable to the present invention, including but not limited to thosedescribed hereinafter.

The polyphenylene ethers comprise a plurality of structural units havingthe formula ##STR1## In each of said units independently, each Q¹ isindependently halogen, primary or secondary lower alkyl (i.e., alkylcontaining up to 7 carbon atoms), phenyl, haloalkyl, aminoalkyl,hydrocarbonoxy, or halohydrocarbonoxy wherein at least two carbon atomsseparate the halogen and oxygen atoms; and each Q² is independentlyhydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl,hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹. Examples ofsuitable primary lower alkyl groups are methyl, ethyl, n-propyl,n-butyl, isobutyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl,2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl and the corresponding heptylgroups. Examples of secondary lower alkyl groups are isopropyl,sec-butyl and 3-pentyl. Preferably, any alkyl radicals are straightchain rather than branched. Most often, each Q¹ is alkyl or phenyl,especially C₁₋₄ alkyl, and each Q² is hydrogen. Suitable polyphenyleneethers are disclosed in a large number of patents.

Both homopolymer and copolymer polyphenylene ethers are included.Suitable homopolymers are those containing, for example,2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers includerandom copolymers containing such units in combination with (forexample) 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable randomcopolymers, as well as homopolymers, are disclosed in the patentliterature.

Also included are polyphenylene ethers containing moieties which modifyproperties such as molecular weight, melt viscosity and/or impactstrength. Such polymers are described in the patent literature and maybe prepared by grafting onto the polyphenylene ether in known mannersuch vinyl monomers as acrylonitrile and vinylaromatic compounds (e.g.,styrene), or such polymers as polystyrenes and elastomers. The producttypically contains both grafted and ungrafted moieties. Other suitablepolymers are the coupled polyphenylene ethers in which the couplingagent is reacted in known manner with the hydroxy groups of twopolyphenylene ether chains to produce a higher molecular weight polymercontaining the reaction product of the hydroxy groups and the couplingagent. Illustrative coupling agents are low molecular weightpolycarbonates, quinones, heterocycles and formals.

The polyphenylene ether generally has a number average molecular weightwithin the range of about 3,000-40,000 and a weight average molecularweight within the range of about 20,000-60,000, as determined by gelpermeation chromatography. Its intrinsic viscosity is most often in therange of about 0.35-0.6 dl./g., as measured in chloroform at 25° C.

The polyphenylene ethers are typically prepared by the oxidativecoupling of at least one corresponding monohydroxyaromatic compound.Particularly useful and readily available monohydroxyaromatic compoundsare 2,6-xylenol (wherein each Q¹ is methyl and each Q² is hydrogen),whereupon the polymer may be characterized as apoly(2,6-dimethyl-1,4-phenylene ether), and 2,3,6-trimethylphenol(wherein each Q¹ and one Q² is methyl and the other Q² is hydrogen).

A variety of catalyst systems are known for the preparation ofpolyphenylene ethers by oxidative coupling. There is no particularlimitation as to catalyst choice and any of the known catalysts can beused. For the most part, they contain at least one heavy metal compoundsuch as a copper, manganese or cobalt compound, usually in combinationwith various other materials.

A first class of preferred catalyst systems consists of those containinga copper compound. Such catalysts are disclosed, for example, in U.S.Pat. Nos. 3,306,874, 3,306,875, 3,914,266 and 4,028,341. They areusually combinations of cuprous or cupric ions, halide (i.e., chloride,bromide or iodide) ions and at least one amine.

Catalyst systems containing manganese compounds constitute a secondpreferred class. They are generally alkaline systems in which divalentmanganese is combined with such anions as halide, alkoxide or phenoxide.Most often, the manganese is present as a complex with one or morecomplexing and/or chelating agents such as dialkylamines, alkanolamines,alkylenediamines, o-hydroxyaromatic aldehydes, o-hydroxyazo compoundsand ω-hydroxyoximes.

Among the polyphenylene ethers which are useful for the purposes of thisinvention are those which comprise molecules having at least one of theend groups of the formulas ##STR2## wherein Q¹ and Q² are as previouslydefined; each R¹ is independently hydrogen or alkyl, with the provisothat the total number of carbon atoms in both R¹ radicals is 6 or less;and each R² is independently hydrogen or a C₁₋₆ primary alkyl radical.Preferably, each R¹ is hydrogen and each R² is alkyl, especially methylor n-butyl.

Polymers containing the aminoalkyl-substituted end groups of formula IIImay be obtained by incorporating an appropriate primary or secondarymonoamine as one of the constituents of the oxidative coupling reactionmixture, especially when a copper- or manganese-containing catalyst isused. Such amines, especially the dialkylamines and preferablydi-n-butylamine and dimethylamine, frequently become chemically bound tothe polyphenylene ether, most often by replacing one of the α-hydrogenatoms on one or more Q¹ radicals. The principal site of reaction is theQ¹ radical adjacent to the hydroxy group on the terminal unit of thepolymer chain. During further processing and/or blending, theaminoalkyl-substituted end groups may undergo various reactions,probably involving a quinone methide-type intermediate of the formula##STR3## with numerous beneficial effects often including an increase inimpact strength and compatibilization with other blend components.Reference is made to U.S. Pat. Nos. 4,054,553, 4,092,294, 4,477,649,4,477,651 and 4,517,341, the disclosures of which are incorporated byreference herein.

Polymers with 4-hydroxybiphenyl end groups of formula IV are typicallyobtained from reaction mixtures in which a by-product diphenoquinone ofthe formula ##STR4## is present, especially in a copper-halide-secondaryor tertiary amine system. In this regard, the disclosures of U.S. Pat.No. 4,477,649 is again pertinent as are those of U.S. Pat. Nos.4,234,706 and 4,482,697, which are also incorporated by referenceherein. In mixtures of this type, the diphenoquinone is ultimatelyincorporated into the polymer in substantial proportions, largely as anend group.

In many polyphenylene ethers obtained under the above-describedconditions, a substantial proportion of the polymer molecules, typicallyconstituting as much as about 90% by weight of the polymer, contain endgroups having one or frequently both of formulas III and IV. It shouldbe understood, however, that other end groups may be present and thatthe invention in its broadest sense may not be dependent on themolecular structures of the polyphenylene ether end groups.

It will be apparent to those skilled in the art from the foregoing thatthe polyphenylene ethers contemplated for use in the present inventioninclude all those presently known, irrespective of variations instructural units or ancillary chemical features.

The poly(alkylene dicarboxylates) useful as reagent B comprise at least30 and most often at least 50 structural units, usually of the formula##STR5## wherein R³ is a divalent aliphatic or alicyclic radicalcontaining about 2-10 carbon atoms and R⁴ is a divalent aliphatic,alicyclic or aromatic radical containing about 2-10 and usually about6-10 carbon atoms. They are typically prepared by the known reaction ofdihydroxy compounds with dicarboxylic acids or functional derivativesthereof such as anhydrides, acid chlorides or lower alkyl (especiallymethyl) esters, preferably the esters.

The R³ radicals may be one or more aliphatic or alicyclic hydrocarbonradicals, alicyclic radicals being known to those skilled in the art tobe equivalent to aliphatic radicals for the purposes of the invention.They may be derived from such dihydroxy compounds as ethylene glycol,1,4-butanediol (both of which are preferred), propylene glycol,1,3-propanediol, 1,6-hexanediol, 1,10-decanediol,1,4-cyclohexanedimethanol and 2-butene-1,4-diol. They may also beradicals containing substituents which do not substantially alter thereactivity of the dihydroxy compound (e.g., alkoxy, halo, nitrile) orhetero atoms (e.g., oxygen or sulfur). The R³ radicals are usuallysaturated.

The R⁴ radicals may be derived from such acids as succinic, adipic,maleic, isophthalic and terephthalic acids or similar substituted andhetero atom-containing acids.

Most often, R³ and R⁴ are hydrocarbon radicals, typically containingabout 2-10 carbon atoms. Preferably, R³ is aliphatic and R⁴ is aromatic.The polyester is most desirably a poly(alkylene terephthalate),particularly poly(ethylene terephthalate) or poly(1,4-butyleneterephthalate) (hereinafter sometimes simply "polyethyleneterephthalate" and "polybutylene terephthalate", respectively) andespecially the latter. Such polyesters are known in the art asillustrated by the following patents:

    ______________________________________                                               2,465,319     3,047,539                                                       2,720,502     3,671,487                                                       2,727,881     3,953,394                                                       2,822,348     4,128,526                                                ______________________________________                                    

The polyesters most often have number average molecular weights in therange of about 10,000-70,000, as determined by intrinsic viscosity (IV)at 30° C. in a mixture of 60% (by weight) phenol and 40%1,1,2,2-tetrachloroethane.

It is also contemplated to employ elastomeric polyesters as reagent B.Such polyesters are known in the art; they are exemplified bycompositions in which a portion of the R³ values are soft segmentradicals such as polyoxyalkylene (typically polyoxyethylene orpolyoxytetramethylene) and units derived from lactones such asε-caprolactone. Numerous elastomeric polyesters of this type arecommercially available; they include those sold by DuPont under thetrademark HYTREL and by General Electric under the trademark LOMOD.

The Z¹ value is a linking group which is usually divalent (as shown informula I) but may also be trivalent, tetravalent, etc., whereupon thecomposition will have multiple polyphenylene ether or polyestermoieties. Its exact molecular structure is not critical from thestandpoint of this invention, since many linking groups are effective toform the desired copolymers. However, it most often has a molecular orformula weight up to about 1500 and preferably up to about 750.Moreover, the fact that only one Z¹ value is shown in formula I does notexclude from the invention compositions in which at least onepolyphenylene ether or polyester moiety contains a plurality of Z¹radicals and associated structure.

Illustrative Z¹ values are single bonds and linkages containing one ormore polyvalent (usually divalent) ether, ester, amide, imide orurethane groups. Also present therein may be one or more polyvalent(usually divalent) aliphatic, alicyclic, heterocyclic or aromaticradicals, including hydrocarbon radicals and substituted hydrocarbonradicals wherein the substituents do not undergo interfering reactionsin the context of the invention. Such linkages may be formed by thereaction of a hydroxy- or carboxy-terminated polyester, a polyphenyleneether and optionally at least one functionalizing agent in which thefunctionality is, for example, one or more epoxide, isocyanate(including masked isocyanate groups such as cyclic urea), cyanurate,isocyanurate, carbodiimide, oxazoline, ester, urethane, carboxylate,carboxy anhydride, carboxamide or carboximide groups.

The copolymer compositions of this invention may be prepared byreactions of polyphenylene ethers with poly(alkylene dicarboxylates).Numerous methods exist for conducting such reactions.

Many of these methods are of particular interest when a functionalizedpolyphenylene ether is employed. These may be prepared by the reactionof at least one functionalizing agent with a polyphenylene ether. Thefunctionality of the functionalized polyphenylene ether may be presenton the end group; for example, as a result of reaction with the phenolicterminal hydroxy group. The hydroxy group in an end group having formulaIV is preferred because of its relative thermal stability.Functionalization may also involve one of the aromatic rings in thepolymer chain, or an alkyl group attached thereto.

One method of functionalizing the polyphenylene ether is by reactionwith at least one compound containing (a) a carbon-carbon double ortriple bond, hydroxy group, alkoxy group, aryloxy group or acyl halidegroup, and also (b) a carboxylic acid, acid salt, acid anhydride, acidamide, acid ester or imido group. A wide variety of such compounds aresuitable for use in the invention. Many illustrative compounds arelisted in U.S. Pat. No. 4,315,086, the disclosure of which isincorporated by reference herein. They include maleic, fumaric, itaconicand citraconic acids and their derivatives, various unsaturated fattyoils and the acids derived therefrom, relatively low molecular weightolefinic acids such as acrylic acid and its homologs, and the like.

Other functionalizing agents of this type are the aliphaticpolycarboxylic acids and derivatives thereof disclosed in copending,commonly owned application Ser. No. 736,489, filed May 20, 1985. Thesecompounds may be represented by the formula

    R.sup.6 OR.sup.5 (COOR.sup.7).sub.p (CONR.sup.8 R.sup.9).sub.s(VIII)

wherein R⁵ is a linear or branched chain saturated aliphatic hydrocarbonof from 2 to 20, preferably 2 to 10, carbon atoms; R⁶ is hydrogen or analkyl or aryl group of 1 to 10, preferably 1 to 6, most preferably 1 to4, carbon atoms, especially hydrogen; each R⁷ is independently hydrogenor an alkyl or aryl group of from 1 to 20 carbon atoms, preferably from1 to 10 carbon atoms; each R⁸ and R⁹ is independently hydrogen or analkyl or aryl group of from 1 to 10, preferably from 1 to 6, mostpreferably 1 to 4, carbon atoms; p and s are each greater than or equalto zero and p+s is at least 2, preferably 2 or 3; and wherein OR⁶ isalpha or beta to a carbonyl group and at least two carbonyl groups areseparated by 2 to 6 carbon atoms.

Illustrative of suitable polycarboxylic acids of this type are citricacid, malic acid, and agaricic acid. Their esters, amides and salts mayalso be used.

Still another class of these functionalizing agents is disclosed incopending, commonly owned application Ser. No. 780,151, filed Sept. 26,1985, the disclosure of which is also incorporated by reference herein.Illustrative compounds within this class are represented by the formula##STR6## wherein R¹⁰ is an aromatic or saturated aliphatic radical, X¹is halogen (especially chlorine) and X² is one or two carboxylic acid,acid salt, acid amide or acid ester groups or a dicarboxylic acidanhydride or imide group. Illustrative compounds of this type arecarboxymethylsuccinic anhydride acid chloride and trimellitic anhydrideacid chloride (TAAC).

Particularly preferred functionalizing agents from this class are maleicacid and its derivatives (especially maleic anhydride), fumaric acid andtrimellitic anhydride acid chloride.

These functionalizing agents may be reacted with the polyphenylene etherby heating a mixture thereof, typically at a temperature within therange of about 80°-390° C., in solution or in the melt and preferablythe latter. In general, about 0.01-2.0, most often about 0.3-1.0 andpreferably about 0.5-1.0 parts (by weight) of said functionalizing agentis employed per 100 parts of polyphenylene ether. The reaction mayconveniently be carried out in an extruder or similar equipment. Certainaspects of the chemistry of polyphenylene ethers so functionalized aredisclosed and claimed in copending, commonly owned application Ser. No.885,497, filed July 14, 1986.

In addition to the above-described functionalizing agents, othercompounds may be used singly or, when appropriate, in combination, forthis purpose. Illustrative functionalizing compounds include thefollowing in addition to those described hereinabove: terephthaloylchloride, isophthaloyl chloride, phthalic anhydride, succinic anhydride,1,1'-terephthaloylbisimidazole, 1,1'-isophthaloylbisimidazole,.di-3-benzisoxazolyl terephthalate, epichlorohydrin, eppxy novolaks,hexamethylene diisocyanate, azelaoylbis(propyleneurea), toluenediisocyanate, tris(6-isocyanatohexyl) isocyanurate,bis(4-isocyanatophenyl)methane, 2,4-bis(4-isocyanatophenylmethyl)phenylisocyanate, 1,2-epoxy-7-octene, glycidyl methacrylate, glycidylacrylate, glycidyl ethyl maleate, glycidyl ethyl fumarate, allylglycidyl ether, diphenylmethane 4,4'-bis(cyclohexylcarbodiimide),1-(t-butylcarbodiimido)-2,4-bis(4-t-butylcarbodiimidophenylmethyl)benzene,di-n-butyl maleate, 1,4-phenylene-bis(2-oxazoline),1,4-butane-bis-(N-isatoic anhydride), terephthaloyl chloride incombination with diols such as 1,4-butanediol and 1,6-hexanediol or withepoxy alcohols such as glycidol, and maleic anhydride in combinationwith hydroxy amines such as ethanolamine or diamines such asethylenediamine.

Many of the functionalized polyphenylene ethers prepared by reactionwith the compounds listed above, and similar compounds, are disclosedand claimed in the following copending, commonly owned applications:

Ser. No. 866,645, filed May 27, 1986, now U.S. Pat. No. 689,372;

Ser. No. 885,112, filed July 14, 1986;

Ser. No. 901,858, filed Aug. 29, 1986;

Ser. No. 912,705, filed Sept. 29, 1986.

The reaction conditions may be chosen so as to promote reactionsinvolving the hydroxy end group of the polyphenylene ether, or reactionsinvolving other portions of the polymer molecule, especially the polymerchain and/or alkyl substituents thereon. The latter may be electrophilicsubstitution reactions involving, for example, N-hydroxyalkyl amides incombination with Lewis acids, or free radical reactions withethylenically unsaturated epoxides.

The free radical reaction may be conducted in solution or in the melt,typically at temperatures in the range of about 100°-350° C. Suitablefree radical initiators include benzoyl peroxide, cumyl peroxide andazobisisobutyronitrile; other conventional initiators known in the artmay also be used, in conventional amounts (typically about 2-15% byweight based on polyphenylene ether).

The above-listed ethylenically unsaturated epoxides are among thosewhich undergo this reaction. The proportion of epoxide used with respectto polyphenylene ether is not critical and depends on the amount offunctionalization desired. It is usually about 10-120% by weight.

It is believed that the functionalization reaction may involveabstraction of a hydrogen atom from an alkyl group on the polyphenyleneether chain to generate a free radical, which reacts with one or moreolefinic moieties in the epoxide to form a monofunctional orpolyfunctional side chain. However, this aspect of the invention is inno way dependent on theory.

It is frequently found that some homopolymerization of the epoxideoccurs simultaneously with functionalization of the polyphenylene ether.Since the presence of homopolymer is not beneficial for the purposes ofthe invention, removal thereof is advisable. It may be achieved byconventional means, typically involving precipitation of a methylenechloride complex of the polyphenylene ether as described by Factor etal. in J. Polymer Sci., Polymer Letters Ed., 7, 205-209 (1969).

The only important consideration is to provide a reactive site on apolyphenylene ether for copolymer formation with the polyester. Theconditions of the reaction providing that site are not a critical aspectof the invention, but may be conventional based on the type of reactioninvolved.

The preparation of functionalized polyphenylene ethers is illustrated bythe following examples. The polyphenylene ether used in each exampleherein, unless otherwise indicated, was an unfunctionalizedpoly-(2,6-dimethyl-1,4-phenylene ether) having a number averagemolecular weight of about 20,000, an intrinsic viscosity (IV) inchloroform at 25° C. of 0.48 dl./g and 0.084% (by weight) hydroxygroups.

EXAMPLE 1

To a solution of 325 grams of polyphenylene ether in 3 liters of toluenewas added a solution of 16.53 grams (81.4 mmol.) of terephthaloylchloride in 250 ml. of toluene. The mixture was stirred for 16 hours,after which 16.7 grams (165 mmol.) of triethylamine was added. Stirringwas continued for 4 hours, after which 15.3 grams (207 mmol.) ofglycidol was added and stirring was continued for 3 days. The productwas precipitated by addition of methanol, redissolved in toluene andreprecipitated, and dried under reduced pressure. It was shown byinfrared spectroscopy to be the desired epoxide-functionalizedpolyphenylene ether, and by analysis to contain 0.0014% (by weight)hydroxy groups.

EXAMPLE 2

Methanesulfonic acid, 617.2 grams (6.43 moles), was added slowly at roomtemperature, with stirring, to a solution of 500 grams of polyphenyleneether in 3.33 liters of chloroform. There was then added over 15minutes, with stirring, a solution of 11.67 grams (131 mmol.) ofN-methylolacetamide in 150 ml. of nitromethane. Stirring was continuedfor 30 minutes, after which the polymer was precipitated by pouring thesolution into methanol. The precipitate was washed with water until thewashings were neutral, redissolved in chloroform, reprecipitated intomethanol, filtered and dried in an oven to yield the desiredamide-functionalized polyphenylene ether.

EXAMPLE 3

A solution of 100 parts of polyphenylene ether, 2 parts of TAAC and 5parts of dimethyl-n-butylamine in 500 parts of toluene was heated at 95°C. for 3 hours, with stirring. Upon precipitation as in Example 1, thedesired anhydride-functionalized polyphenylene ether was obtained. Itsstructure was confirmed by infrared spectroscopy.

EXAMPLE 4

Cyclohexylamine, 8.64 grams (87 mmol.), was added dropwise undernitrogen, with stirring, to a solution of 10 grams (26.2 mmol.) of1-isocyanato-2,4-bis(4-isocyanatophenylmethyl)benzene in 200 ml. of drytoluene. The mixture was heated for 1 hour at 80° C., with stirring, andcooled to room temperature. The precipitated solid was filtered, washedwith toluene and dried. Based on method of preparation, it was atris-urea of the formula ##STR7##

To a mixture of 4 grams of the tris-urea in 12 ml. of dry pyridine wasadded portionwise 6 grams of p-toluenesulfonyl chloride. The mixture washeated under nitrogen at 70° C. for 1 hour and poured into 30 ml. of icewater, with vigorous stirring. Ethyl acetate, 40 ml., was added and themixture was stirred for 10 minutes. The aqueous layer was removed andthe organic layer was washed with aqueous sodium carbonate solution andvacuum stripped. The residue was extracted twice with petroleum ether toyield the desired1-cyclohexylcarbodiimido-2,4-bis(4-cyclohexylcarbodiimidophenylmethyl)benzene.

To a solution of 500 grams of the anhydride-functionalized polyphenyleneether of Example 3 in 3.2 liters of dry toluene was added undernitrogen, with stirring, a solution of 58 grams of the tris-carbodiimideprepared as described above. The mixture was heated under reflux for 4hours in a nitrogen atmosphere, cooled and poured into a large excess ofacetone. The desired carbodiimide-functionalized polyphenylene ether wasfiltered, washed with acetone and dried.

EXAMPLES 5-8

Various monomeric epoxides, in combination with dicumyl peroxide (4.3%by weight based on polyphenylene ether in Examples 5-7, 6% in Example 8)as a free radical initiator, were added to 10% (weight/volume) solutionsof polyphenylene ether in chlorobenzene. The solutions were heated toreflux for 3 hours under nitrogen, with stirring, and the crudeepoxide-functionalized polymers were cooled and precipitated withmethanol. They were purified by dissolving at a level of about 10% byweight in methylene chloride, allowing the solution to stand until themethylene chloride complex had precipitated, filtering, washing withmethylene chloride and drying in an oven. The relevant parameters aregiven in Table I.

                  TABLE I                                                         ______________________________________                                        Monomer                                                                                                Amt.(ml. per g.                                                               polyphenylene                                        Example   Identity       ether)                                               ______________________________________                                        5         Glycidyl methacrylate                                                                        0.56                                                 6         Glycidyl acrylate                                                                            0.17                                                 7         Allyl glycidyl ether                                                                         0.5                                                  8         1,2-Epoxy-7-octene                                                                           1.0                                                  ______________________________________                                    

EXAMPLE 9

To a solution of 12.5 grams of polyphenylene ether in 125 ml. of toluenewas added under nitrogen, with stirring, 7 ml. of glycidyl methacrylateand 0.48 gram of benzoyl peroxide. The mixture was heated under refluxfor 3 hours and the epoxide-functionalized polyphenylene ether wasisolated as in Examples 5-8.

EXAMPLE 10

A mixture of 970 grams of polyphenylene ether and 30 grams of mixedglycidyl ethyl maleate and glycidyl ethyl fumarate was extruded on atwin-screw extruder at 290° C. The resulting epoxy-functionalizedpolyphenylene ether was purified by reprecipitation from toluene withmethanol, formation of the methylene chloride complex and thermaldecomposition thereof as in Examples 5-8.

EXAMPLE 11

A mixture of 2.2 grams of polyphenylene ether, 0.5 ml. of glycidylmethacrylate and 0.1 gram of benzoyl peroxide was heated at 320°-330° C.under nitrogen for 5 minutes, with gentle stirring. Upon dissolution intoluene, reprecipitation with methanol, washing with methylene chlorideand drying, there was obtained the desired epoxide-functionalizedpolyphenylene ether.

EXAMPLE 12

A mixture of 99 parts of polyphenylene ether and 1 part of maleicanhydride was extruded on a single-screw extruder at temperatures in therange of 120°-330° C. The extrudate, comprising ananhydride-functionalized polyphenylene ether, was quenched in water,pelletized, dissolved in chloroform, precipitated with methanol,filtered and vacuum dried at 60° C.

EXAMPLES 13-16

Blends of polyphenylene ether with maleic anhydride or dibutyl maleatewere prepared in a Henschel mixer and extruded on a twin-screw extruder.The extrudates, constituting the desired anhydride- andester-functionalized polyphenylene ethers, were quenched in a water bathand pelletized. The details are given in Table II, all parts being byweight.

                  TABLE II                                                        ______________________________________                                        Reagent                                                                                           Amt.                                                                          (parts per 100 parts                                                                         Extrusion                                  Example                                                                              Identity     polyphenylene ether)                                                                         temp., °C.                          ______________________________________                                        13     Maleic anhydride                                                                           0.5            330*                                       14     Dibutyl maleate                                                                            1              330*                                       15     "            2              310                                        16     "            5              310                                        ______________________________________                                         *Temperature of extruder walls.                                          

EXAMPLES 17-21

Hydroxyalkyl-functionalized polyphenylene ethers were prepared by thereaction of various poly(2,6-dimethyl-1,4-phenylene)ethers withterephthaloyl chloride and 1,4-butanediol or 1,6-hexanediol, accordingto the following procedure.

A solution of the polyphenylene ether in toluene was distilled to removeabout 75 ml. of toluene and any water or other volatiles. The solutionwas cooled to 70° C. and terephthaloyl chloride was added, after whichthe solution was stirred at the same temperature for 2 hours.Triethylamine was added and the mixture was stirred overnight. Asolution of the diol in 150 ml. of chloroform was then added andstirring was continued at 70° C. for 4 hours. Thehydroxyalkyl-functionalized polyphenylene ether was precipitated withmethanol, dissolved in chloroform, reprecipitated with methanol anddried under vacuum at 60° C.

The compositional details and other parameters are given in Table III.

                                      TABLE III                                   __________________________________________________________________________                                        Diol     Product                          Polyphenylene ether                                                                          Toluene,                                                                           Terephthaloyl                                                                         Triethylamine,                                                                        No. of                                                                             Amt.,  % OH                          Example                                                                            IV, dl./g.                                                                         Amt., g.                                                                           I.   chloride, g.                                                                          g.      carbons                                                                            g.  IV by Wt.                        __________________________________________________________________________    17   0.51 325  3.0  16.9    18.6    4    40  0.54                                                                             0.053                         18   0.51 456  3.75 23.8    25.0    4    58  -- --                            19   0.51 456  3.75 32.8    34.2    4    78  0.48                                                                             0.039                         20   0.43 440  3.75 31.6    31.5    6    99     0.038                         21   0.43 469  3.75 24.4    25.4    6    75  0.50                                                                             0.035                         __________________________________________________________________________

EXAMPLE 22

Ethanolamine, 0.2 ml., was added to a solution of 19.41 grams of theanhydride-functionalized polyphenylene ether of Example 13 in 100 ml. ofo-dichlorobenzene. The solution was heated at 170° under nitrogenovernight, with stirring. The N-hydroxyalkylimide-functionalizedpolyphenylene ether was precipitated with methanol, reprecipitated threetimes from chloroform with methanol and dried under vacuum.

EXAMPLE 23

Ethylenediamine, 3 ml., was added to a solution of 10 grams of theanhydride-functionalized polyphenylene ether of Example 13 in 100 ml. oftoluene, while said solution was maintained at reflux under nitrogen.Refluxing was continued for 6 hours, after which theN-aminoalkylimide-functionalized polyphenylene ether was precipitated byaddition of methanol, reprecipitated from chloroform with methanol, anddried at 60° in vacuum.

EXAMPLES 24-25

Examples 24-26 describe the preparation of bis(hydroxyalkyl) maleatesand fumarates used in the preparation of hydroxyalkyl-functionalizedpolyphenylene ethers.

Titanium(IV) isopropoxide was added at 165° C. to a mixture of dimethylmaleate and 1,4-butanediol. Heating at this temperature was continued tocomplete esterification, with removal of by-product methanol bydistillation. When methanol removal was complete, any excess diol wasremoved by vacuum stripping to yield the desired bis(hydroxyalkyl)maleates. The details of their preparation are given in Table IV.

                  TABLE IV                                                        ______________________________________                                                      Diol                                                                   Dimethyl     No. of   Amt., Ti(OC.sub.3 H.sub.7).sub.4,                Example                                                                              maleate, moles                                                                             carbons  moles ml.                                        ______________________________________                                        24     0.368        4        2.18  0.2                                        25     1.96         4        3.55  0.15                                       ______________________________________                                    

EXAMPLE 26

A solution of 0.1 mole of fumaryl chloride in 40 ml. of methylenechloride was added dropwise at 5°-10° C. over 2 hours under nitrogen,with stirring, to a suspension of 0.8 mole of 1,6-hexanediol in 1 literof methylene chloride. There was simultaneously added a solution of 0.21mole of sodium hydroxide in 50 ml. of water. The mixture was stirred andallowed to warm to room temperature and the organic layer was separated,filtered through magnesium sulfate and vacuum stripped. Unreacted1,6-hexanediol was removed by vacuum distillation. The residue was thedesired bis(6-hydroxyhexyl) fumarate.

EXAMPLES 27-34

Polyphenylene ethers were dry blended with the above bis(hydroxyalkyl)maleates and the blends were extruded in a twin-screw extruder, withvacuum venting. The extrudates, constituting the desiredhydroxyalkyl-functionalized polyphenylene ethers, were quenched in waterand pelletized. The details of functionalization are given in Table V.

                  TABLE V                                                         ______________________________________                                                                    Parts maleate                                            Maleate  Polyphenylene                                                                             per 100 parts                                                                           Extruder                                       of       ether       polyphenylene                                                                           temp.,                                  Example                                                                              Example  IV, dl./g.  ether     °C.                              ______________________________________                                        27     24       0.5         1         275                                     28     24       0.5         2         275                                     29     24       0.5         5         275                                     30     25       0.4         2         285                                     31     25       0.5         2         290                                     32     26       0.5         2.5       293                                     33     26       0.5         1         293                                     34     26       0.5         5         293                                     ______________________________________                                    

The copolymers of this invention may be prepared by a number of methods.These include reactions of unfunctionalized or (preferably)hydroxyalkyl-functionalized (includingN-hydroxyalkylimide-functionalized) polyphenylene ethers with preformedpolyesters containing carboxy end groups, or with one or more precursorsof such polyesters, to produce copolymers in which Z¹ is a single bondor contains at least one ester group. Conversely, a hydroxy-terminatedpolyester may be reacted with a carboxy-functionalized (e.g., byreaction with maleic anhydride, fumaric acid or TAAC) polyphenyleneether. These reactions are straightforward and are conducted underconventional esterification conditions.

Reactions involving polyester precursors are often particularly usefulwhen the reaction of a functionalized or unfunctionalized polyphenyleneether with a polyester would produce a copolymer with an undesirably lowmolecular weight of the polyester portion. This sometimes occurs becauseof molecular weight degradation of the polyester upon reaction with thepolyphenylene ether.

In one polyester precursor method, a polyphenylene ether, preferablyhydroxyalkyl-functionalized, is incorporated in a conventionalpolyester-forming reaction. As previously noted, such reactionsordinarily involve dihydroxy compounds and dicarboxylic acids orfunctional derivatives thereof, preferably lower alkyl and especiallymethyl esters.

In a second method, a polyester oligomer, generally containing up toabout 25 structural units, is initially formed and subsequently reactedwith a hydroxyalkyl-terminated polyphenylene ether. This process, likethe first, utilizes conventional polyester-forming conditions.

It is also within the scope of the invention to react otherfunctionalized polyphenylene ethers as described hereinabove with atleast one preformed poly(alkylene dicarboxylate) to prepare copolymercompositions of this invention. This reaction may be conducted insolution or in the melt, generally at temperatures within the range ofabout 100°-300° and preferably about 150°-290° C. Depending on thenature of the functionalization, it may be necessary or preferred toemploy at least one catalyst in the reaction; suitable catalysts will beapparent to those skilled in the art upon consideration of thefunctional groups to be reacted.

It is sometimes advantageous to prepare a functionalized polyester forreaction with a functionalized or unfunctionalized polyphenylene ether.Polyesters containing amine or isocyanate end groups are particularlyuseful; amine-functionalized polyesters are disclosed, for example, inU.S. Pat. No. 4,436,895. Therefore, another aspect of the presentinvention is amine- and isocyanate-terminated poly(alkylenedicarboxylates). For the most part, such polyesters comprise repeatingunits of formula VII and end groups of the formula ##STR8## wherein R³and R⁴ are as previously defined, X³ is NH² or ##STR9## n is 0 or 1 andZ³ is a divalent aliphatic or aromatic radical.

The Z³ value may be any aliphatic or aromatic radical present in apolyisocyanate, most often a diisocyanate. It is usually an alkylene orarylene radical, most often hexamethylene, tolylene orp,p'-diphenylenemethane.

The value of n will depend on whether the functionalized polyester isprepared from a hydroxy- or carboxy-terminated polymer. Hydroxy groupsreact with diisocyanates to produce isocyanato carbamates and with aminoacids to form amino esters, and therefore n will be 0 in the case ofhydroxy termination. On the other hand, carboxylic acid groups reactwith diisocyanates with decarboxylation to form isocyanato amides,whereupon n will be 1.

The preparation of the amine- or isocyanate-terminated polyester may beachieved by reaction of the polyester with an amino acid, amino ester orpolyisocyanate (usually a diisocyanate) in the melt or in solution.Temperatures in the range of about 100°-175° C. are usually adequate.Preparation by incorporation of an amino acid or amino ester in aconventional polyester-forming reaction as an endcapping agent is alsocontemplated.

The preparation of the amine- or isocyanate-terminated polyesters ofthis invention is illustrated by the following examples. Unlessotherwise indicated, the polyester used in these and other examples wasa polybutylene terephthalate having a number average molecular weight ofabout 40,000 and a carboxy end group concentration of 24.7microequivalents per gram.

EXAMPLE 35

A solution of 20 grams of polyester in 200 ml. of dry1,1,2,2-tetrachloroethane was heated to 140° C. under nitrogen and 6 ml.of hexamethylene diisocyanate was added. Heating and stirring undernitrogen were continued for 3 days; the solution was then diluted with300 ml. of dry acetone and the precipitated product was filtered, washedwith acetone, reprecipitated twice more in the same way and dried undervacuum. Upon reaction of a portion of the product with n-octadecanol andspectroscopic analysis, it was found that all of the hydroxy end groupsand more than 90% of the carboxy end groups had been functionalized withisocyanate.

EXAMPLE 36

Following substantially the procedure of Example 35, anisocyanate-functionalized polyester was prepared from a polybutyleneterephthalate oligomer having a number average molecular weight of about4,000.

EXAMPLE 37

A mixture of 300 grams of 1,4-butanediol, 388 grams of dimethylterephthalate, 7.3 grams of ethyl 4-aminobenzoate and 0.5 ml. oftetra-2-ethylhexyl titanate was heated with stirring as methanol wasremoved by distillation. The residue after complete removal of methanolwas the desired amine-functionalized polyester.

Still another method for preparing the copolymer compositions of thisinvention is to blend the polyphenylene ether (which may befunctionalized or unfunctionalized), polyester and at least onefunctionalizing agent and then heat the blend, in solution or in themelt, under conditions similar to those described hereinabove for thefunctionalized polyphenylene ether-polyester reaction. Saidfunctionalizing agent then reacts substantially simultaneously with bothpolymers, yielding the desired copolymer composition.

In general, the copolymer compositions of this invention comprise onlypartially copolymer, with the balance being a polyphenyleneether-polyester blend. The approximate proportion of copolymer in thecomposition may often be conveniently expressed as the percentage ofcopolymerized polyphenylene ether based on total polyester. It may bedetermined by extracting unreacted polyphenylene ether with a suitablesolvent, typically toluene, and analyzing the insoluble residue(copolymer and residual polyester) by proton nuclear magnetic resonance.

If the functionalizing agent is one which reacts more favorably withcarboxy end groups then with hydroxy end groups, it is frequentlypreferred to maximize the proportion of carboxy end groups in thepolyester. This may frequently be accomplished by pre-extruding thepolyester, typically at a temperature in the range of about 250°-300° C.Under these conditions, there is apparently a loss by degradation andvolatilization of hydroxy end group functionality, producing a polymerwith a high proportion of carboxy end groups.

The preparation of polyphenylene ether-polyester copolymer compositionsof this invention is illustrated by the following examples.

EXAMPLE 38

A solution of 20 grams of the hydroxyalkyl-functionalized polyphenyleneether of Example 17, 32.2 grams of dimethyl terephthalate, 16.4 grams of1,4-butanediol and 0.18 ml. of tetraisopropyl titanate in 40 ml. of1,2,4-trichlorobenzene was heated at 170° C., with stirring, as methanolwas removed by distillation. When 10 grams of methanol had been removed,the temperature was increased to 255° C. and vacuum was applied toremove trichlorobenzene and excess diol. The resulting melt was stirredat 255° C. for 11/2 hours at 0.1 torr to produce the desiredpolyphenylene ether-polybutylene terephthalate copolymer.

EXAMPLE 39

A mixture of 79 grams of dimethyl terephthalate, 63 grams of1,4-butanediol and 0.1 ml. of tetra-2-ethylhexyl titanate was heated at165-235° C. as methanol was removed by distillation, and then undervacuum for 1/2 hour at 250°-265° C. There was then added, undernitrogen, 60 grams of the hydroxyalkyl-functionalized polyphenyleneether of Example 20. The mixture was stirred at 250°-265° C. undernitrogen for 5 minutes and under reduced pressure for 30 minutes. Uponanalysis, it was shown that about 7% of the polyphenylene ether wascopolymerized.

EXAMPLE 40

To a solution of 50 grams of polyphenylene ether in 700 ml. of1,2,4-trichlorobenzene was added 985 mg. of maleic anhydride. Themixture was stirred until dissolution took place, whereupon 750 ml. of3-amino-1-propanol was added. Stirring was continued for one hour, afterwhich 43.6 grams each of dimethyl terephthalate and 1,4-butanediol wereadded. The mixture was heated to 145° C., with stirring, and 0.15 ml. oftetra-2-ethylhexyl titanate was added. Heating was continued and thetemperature increased to 190° C., whereupon methanol was removed bydistillation. When a major proportion of volatile materials (methanol,1,4-butanediol and trichlorobenzene) had been removed by distillation,the mixture was vacuum stripped to yield the desired polyphenyleneether-polyester copolymer.

EXAMPLE 41

A solution of 250 grams of polyester in 3.8 liters of1,2,4-trichlorobenzene was heated to 200° C. and 250 grams of theepoxide-functionalized polyphenylene ether of Example 1 was added undernitrogen, with stirring. Stirring at 200° C. was continued for 60 hours,after which the copolymer composition was precipitated by pouring intoacetone, extracted with methanol and dried under vacuum. Analysis showedthe presence of 28% copolymerized polyphenylene ether.

EXAMPLE 42

The procedure of Example 41 was repeated, using a polyester which hadbeen preextruded on a twin-screw extruder at about 260° C., and whichhad a carboxylate end group concentration of 34.3 microequivalents pergram. Analysis showed the presence of 39% copolymerized polyphenyleneether.

EXAMPLE 43

A solution of 150 grams of the preextruded polyester of Example 42 in2.25 liters of 1,2,4-trichlorobenzene was heated to 200° C. undernitrogen, and 150 grams of the carbodiimide-functionalized polyphenyleneether of Example 4 was added. Heating was continued for 2 hours at 190°C. The solution was then poured into acetone and the precipitatedcopolymer composition filtered and extracted with acetone. Analysisshowed the presence of 61% copolymerized polyphenylene ether.

EXAMPLES 44-48

A mixture of 2 grams of the polybutylene terephthalate oligomer used asa reactant in Example 36, 2 grams of functionalized polyphenylene ether,0.1 ml. of titanium(IV) isopropoxide and 40 ml. of1,2,4-trichlorobenzene was heated at 200°-220° C. for 3-4 hours.Toluene, 100 ml., was added carefully and the mixture was heated underreflux for 1/2) hour, whereupon the copolymer composition precipitated.It was isolated by centrifugation, washed with toluene, centrifugedagain and dried at 60° C. under vacuum. The products were analyzed byproton nuclear magnetic resonance to determine the amount ofcopolymerized polyphenylene ether. The results are given in Table VI(PPE=polyphenylene ether).

                  TABLE VI                                                        ______________________________________                                                  Functionalized PPE                                                                          % copolymerized                                       Example   of Example    PPE                                                   ______________________________________                                        44         3            13                                                    45        13            16                                                    46        14            19                                                    47        15            19                                                    48        16            20                                                    ______________________________________                                    

EXAMPLES 49-58

Solutions of 10 grams of functionalized polyphenylene ether and 10 gramsof polyester in 200 ml. 1,2,4-trichlorobenzene were heated to 220° C.and 0.1 ml. of titanium(IV) isopropoxide was added. Heating wascontinued under nitrogen, with stirring, with samples being periodicallyremoved and analyzed for copolymer formation. The results are given inTable VII.

                  TABLE VII                                                       ______________________________________                                                  Functionalized PPE                                                                          % copolymerized                                       Example   of Example    PPE                                                   ______________________________________                                        49        17            56                                                    50        21            26                                                    51        27            15                                                    52        28            31                                                    53        29            36                                                    54        30            21                                                    55        31            21                                                    56        32            30                                                    57        33            14                                                    58        34            46                                                    ______________________________________                                    

EXAMPLE 59

A solution in 85 ml. of 1,2,4-trichlorobenzene of 5 grams of theanhydride-functionalized polyphenylene ether of Example 12, 5 grams of apolybutylene terephthalate having a weight average molecular weight ofabout 25,000 which had been preextruded at temperatures in the range of120°-260° C., and 5 grams of an epoxy novolak commercially availablefrom Dow Chemical Company under the designation "D.E.N. 485" was heatedat 200° C., under nitrogen, for 16 hours. Toluene, 100 ml., was addedand the mixture was heated under reflux for 1/2 hour and cooled. Thepolyphenylene ether-polyester copolymer was removed by centrifugation,washed with toluene and again centrifuged. Analysis showed the presenceof 10% copolymerized polyphenylene ether.

EXAMPLES 60-69

Solutions of 5 grams each of various polyphenylene ethers and polyestersand, optionally, 5 grams of various polyisocyanates or maskedpolyisocyanates in 50 ml. of various solvents were heated undernitrogen, with stirring, for 20 hours. The mixtures were then dilutedwith 50 ml. of toluene, boiled for 30 minutes and cooled. Theprecipitates were separated by centrifugation, washed with toluene anddried and the proportions of copolymer therein were determined aspreviously described.

The relevant parameters and copolymer proportions are given in TableVIII. Functionalized polyphenylene ethers and polyesters are identifiedby example numbers, unfunctionalized polyphenylene ether as "Unfunc."and unfunctionalized polybutylene terephthalate by molecular weight. Theisocyanate compounds used were:

(I) Hexamethylene diisocyanate

(II) Azelaoyl bispropylene urea

(III) Tris(6-isocyanatohexyl) isocyanurate.

                                      TABLE VIII                                  __________________________________________________________________________         Polyphenylene                   Temp.,                                                                            % copolymerized                      Example                                                                            ether   Polyester                                                                          Isocyanate                                                                          Solvent      °C.                                                                        PPE                                  __________________________________________________________________________    60     Unfunc.                                                                              4,000                                                                                 I 1,2,4,-Trichlorobenzene                                                                    180 25                                   61   Ex. 3    4,000                                                                                 I 1,1,2,2-Tetrachloroethane                                                                  140 31                                   62   Ex. 2    4,000                                                                                 I 1,2,4-Trichlorobenzene                                                                     180 55                                   63   Ex. 3   50,000                                                                                 I Nitrobenzene 170  5                                   64   Ex. 2   50,000                                                                               II  1,2,4-Trichlorobenzene                                                                     220 20                                   65   Ex. 3   Ex. 36                                                                             --    1,1,2,2-Tetrachloroethane                                                                  140 38                                   66   Ex. 3   Ex. 35                                                                             --    Nitrobenzene 170 24                                   67   Ex. 2   Ex. 35                                                                             --    1,2,4-Trichlorobenzene                                                                     200 58                                   68     Unfunc.                                                                             50,000                                                                             III   1,2,4-Trichlorobenzene                                                                     200  8                                   69   Ex. 3   50,000                                                                             III   1,2,4-Trichlorobenzene                                                                     200 17                                   __________________________________________________________________________

EXAMPLES 70-71

Mixtures of equal weights of various polyphenylene ethers, polyester andtris(6-isocyanatohexyl) isocyanurate were extruded at 270° C. on atwin-screw extruder. The proportions of copolymer in the extrudates weredetermined as previously described. The results are given in Table IX.

                  TABLE IX                                                        ______________________________________                                                   Polyphenylene                                                                             % copolymerized                                        Example    ether       PPE                                                    ______________________________________                                        70         Unfunc.     18                                                     71         Ex. 3       23                                                     ______________________________________                                    

EXAMPLES 72-92

Solutions of 5 grams each of polyester, unfunctionalized orfunctionalized polyphenylene ether and various coupling agents andcondensation catalysts in 50 ml. of dry 1,2,4-trichlorobenzene wereheated under nitrogen at 200° C. for two hours, diluted with 50 ml. oftoluene and boiled for 30 minutes. The mixtures were cooled andcentrifuged and the solids removed by centrifugation were washed withtoluene and dried.

The coupling agents and catalysts are identified as follows:

Coupling agents

(IV) 1,4-Bis(2-oxazolinyl)benzene

(V) 1,4-Butylene-bis(N-isatoic anhydride)

(VI) Bis(4-isocyanatophenyl)methane

(VII) 1,4-Benzene diisocyanate

(VIII) 2,4-Bis(4-isocyanatophenylmethyl)phenyl isocyanate

Catalysts

(IX) Zinc acetate

(X) Dibutyltin diacetate

(XI) p-Dimethylaminopyridine

(XII) 1-Phenyl-3-methylphospholene oxide

(XIII) 1,3-Dimethylphospholene oxide

(XIV) Trimethylphosphine oxide

(XV) Triethylphosphine oxide.

The relevant parameters are given in Table X. Proportions of couplingagents and catalysts are in mole percent based on end groupconcentration of the polyphenylene ether.

                                      TABLE X                                     __________________________________________________________________________    Polyphenylene                                                                              Coupling agent                                                                          Catalyst  % copolymerized                              Example                                                                            ether   Identity                                                                           Mole %                                                                             Identity                                                                           Mole %                                                                             PPE                                          __________________________________________________________________________    72   Ex. 3   IV   1.0  --   --    9                                           73   Ex. 3   IV   1.0  IX   0.1  12                                           74   Ex. 3   IV   1.0    X  0.1  20                                           75   Ex. 12  IV   1.0  --   --    8                                           76   Ex. 12  IV   1.0  IX   0.1  10                                           77   Ex. 12  IV   1.0    X  0.1  29                                           78   Unfunc. IV   1.0  --   --    6                                           79   Unfunc. IV   1.0  IX   0.1   6                                           80   Unfunc. IV   1.0    X  0.1  11                                           81   Unfunc.   V  1.0  XI   0.5  12                                           82   Unfunc.   V  1.0  XI   1.0  18                                           83   Unfunc.   V  1.5  XI   1.5  18                                           84   Unfunc.   V  2.0  XI   2.0  22                                           85   Ex. 3   VI   1.0  XV.sup.                                                                            0.1  11                                           86   Ex. 3   VI   1.0  XIV.sup.                                                                           0.1  27                                           87   Ex. 3   VI   1.0  XII  0.1  28                                           88   Ex. 3   VI   1.0  XIII 0.1  29                                           89   Ex. 12  VI   1.0  XV   0.1  24                                           90   Ex. 12  VI   1.0  XII  0.1  35                                           91   Ex. 3   VII  2.0  XIII 0.1  32                                           92   Ex. 3   VIII 1.4  XIII 0.1  29                                           __________________________________________________________________________

EXAMPLE 93

A mixture of 50 grams each of polyester and thehydroxyalkyl-functionalized polyphenylene ether of Example 17 was heatedto 250° C. in a nitrogen-filled Helicone reactor, and 0.2 ml. oftetraisopropyl titanate was added. The mixture was heated and stirredfor 1/2 hour. There was obtained the desired copolymer containing 27%copolymerized polyphenylene ether.

EXAMPLE 94

A solution of one gram each of polyester and the epoxy-functionalizedpolyphenylene ether of Example 10 in 25 ml. of 1,2,4-trichlorobenzenewas heated under reflux for two days and cooled. Unreacted polyphenyleneether was removed as previously described, yielding the desiredcopolymer composition containing 40% copolymerized polyphenylene ether.

EXAMPLE 95

A solution of 150 grams each of polyphenylene ether and polyester in 2liters of 1,2,4-trichlorobenzene was distilled until about 100 ml. ofdistillate had been collected. It was then cooled to 160° C. and therewere added dropwise 52 ml. of diphenyl chlorophosphate followed by amixture of 54 ml. of pyridine and 37.8 ml. of triethylamine. Thesolution was heated under reflux for 3 hours and cooled, and the solidswere precipitated with methanol, filtered, washed with methanol andextracted twice by boiling with 3 liters of toluene, cooling andfiltering. The remaining solid was dissolved in 3 liters of boilingchloroform, precipitated with methanol and dried under vacuum to yieldthe desired, copolymer composition. Analysis showed the presence of 18%copolymerized polyphenylene ether.

EXAMPLE 96

A solution of 10 grams each of polyphenylene ether and polyester in 200ml. of 1,2,4-trichlorobenzene was heated under nitrogen and 1 gram of1,2-benzisoxazol-3-yl diphenyl phosphate was added, followed by 0.11 ml.of tri-n-butylamine. The solution was heated under reflux for 24 hours,cooled and poured into 2 volumes of acetone. The copolymer compositionwas filtered, washed with acetone and dried in a vacuum oven. Analysisshowed the presence of 12% copolymerized polyphenylene ether.

EXAMPLES 97-99

Solutions of 10 grams each of polyphenylene ether and polyester and 1gram of a coupling agent in 200 ml. of 1,2,4-trichlorobenzene wereheated under reflux for various periods and the copolymer compositionswere isolated as in Example 98. The coupling agents used were:

(XVI) 1,1'-terephthaloylbisimidazole

(XVII) 1,1'-isophthaloylbisimidazole

(XVIII) di-3-benzisoxazolyl terephthalate.

The relevant parameters are given in Table XI.

                  TABLE XI                                                        ______________________________________                                                 Coupling   Reaction % copolymerized                                  Example  agent      time, hrs.                                                                             PPE                                              ______________________________________                                        97       XVI        24       14                                               98       XVII        3       10                                               99       XVIII      22       12                                               ______________________________________                                    

EXAMPLES 100-104

Various functionalized polyphenylene ethers were heated under reflux for48 hours in a nitrogen atmosphere with an equal weight of polyester in1,2,4-trichlorobenzene solution. The products were isolated byprecipitation into acetone and extraction with toluene as previouslydescribed. The results of analysis are given in Table XII.

                  TABLE XII                                                       ______________________________________                                                  Functionalized PPE                                                                          % copolymerized                                       Example   of Example    PPE                                                   ______________________________________                                        100       5             17                                                    101       7             18                                                    102       8             22                                                    103       9             17                                                    104       11            25                                                    ______________________________________                                    

As previously mentioned, the polyphenylene ether-poly(alkylenedicarboxylate) copolymer compositions of this invention, andpolyphenylene ether-poly(alkylene dicarboxylate) blends in which theyare incorporated, have high impact strength, good solvent resistance andother advantageous properties. These properties make them useful for thepreparation of molded and extruded articles.

The weight ratio of polyester to polyphenylene ether in thecopolymer-containing blend is generally in the range of about 0.5-3.0:1,most often about 0.9-2.5:1. The proportion of copolymerizedpolyphenylene ether therein is capable of wide variation, essentiallyany quantity thereof affording some improvement in properties. For themost part, said proportion is in the range of about 10-80% by weight oftotal resinous components.

The blends may also contain ingredients other than the copolymer,polyphenylene ether and polyester. A particularly useful otheringredient in many instances is at least one elastomeric impact modifierwhich is compatible with the polyphenylene ether. It is generallypresent in the amount of about 5-25% by weight of resinous components.

Suitable impact modifiers include various elastomeric copolymers, ofwhich examples are ethylene-propylenediene polymers (EPDM's), bothunfunctionalized and functionalized with (for example) sulfonate orphosphonate groups; carboxylated ethylene-propylene rubbers; copolymers(usually block or graft) of alkenylaromatic compounds such as styreneand/or epoxy compounds such as glycidyl methacrylate with polymerizableolefins or dienes, including butadiene, isoprene, chloroprene, ethylene,propylene and butylene; and core-shell elastomers containing, forexample, a poly(alkyl acrylate) core attached to a polystyrene shell viaan interpenetrating network. Such core-shell elastomers are more fullydisclosed in copending, commonly owned application Ser. No. 811,808,filed Dec. 20, 1985, now U.S. Pat. No. 4,681,915.

The preferred impact modifiers are block (typically diblock, triblock orradial teleblock) copolymers of alkenylaromatic compounds and olefins ordienes. Most often, at least one block is derived from styrene and atleast one other block from at least one of butadiene, isoprene, ethyleneand butylene. Especially preferred are the triblock copolymers withpolystyrene end blocks and olefin- or diene-derived midblocks. When oneof the blocks is derived from one or more dienes, it is frequentlyadvantageous to reduce the aliphatic unsaturation therein by selectivehydrogenation. The weight average molecular weights of the impactmodifiers are typically in the range of about 50,000-300,000. Blockcopolymers of this type are commercially available from Shell ChemicalCompany under the trademark KRATON, and include KRATON D1101, G1650,G1651, G1652, G1657 and G1702.

Other conventional ingredients which may be present in thecopolymer-containing blends include fillers, flame retardants,colorants, stabilizers, antistatic agents, mold release agents and thelike, used in conventional amounts. The presence of other resinouscomponents is also contemplated. These include impact modifierscompatible with the polyester, such as various graft and core-shellcopolymers of such monomers as butadiene, styrene, butyl acrylate andmethyl methacrylate. The presence of such copolymers frequently improvesthe low-temperature ductility of the blends.

The preparation of copolymer-containing blends is normally achievedunder conditions adapted for the formation of an intimate resin blend.Such conditions often include extrusion, typically at temperatures inthe range of about 100°-300° C. and otherwise under the conditionspreviously described. Extrusion may be conveniently effected in ascrew-type or similar extruder which applies a substantial shearingforce to the composition, thereby decreasing the particle size thereof.It is sometimes found that the impact strength of the composition isincreased if it is extruded more than once, thereby insuring effectiveblending.

The preparation and properties of blends containing the copolymers ofthis invention in combination with impact modifiers are illustrated bythe following examples.

EXAMPLES 105-111

Resin blends were prepared by extrusion under conventional conditions ina twin-screw extruder. The impact modifier ("SEBS") in each blend was acommercially available triblock copolymer in which the polystyrene endblocks have weight average molecular weights of 29,000 and theethylene/butylene midblock has a weight average molecular weight of116,000.

The relevant proportions and parameters are given in Table XIII. Allingredient percentages are by weight. Polyesters are identified as "PET"(polyethylene terephthalate) or "PBT" (polybutylene terephthalate) andby number average molecular weight. Tensile strength and modulus valuesare in pascals×10⁻⁷.

                                      TABLE XIII                                  __________________________________________________________________________    Example             105                                                                              106                                                                              107                                                                              108                                                                              109                                                                              110                                                                              111                                     __________________________________________________________________________    Copolymer-containing composition, %:                                          Example 41          75.4                                                                             -- -- -- -- -- --                                      Example 43          -- -- -- -- 64.4                                                                             -- --                                      Polyphenylene ether, %:                                                       Unfunc.             0.5                                                                              -- -- -- 12.75                                                                            -- --                                      Example 4           -- -- -- -- -- 45 45                                      Example 5           -- 36 -- -- -- -- --                                      Example 6           -- -- 36 36 -- -- --                                      Polyester, %:                                                                 PBT, 40,000         14.1                                                                             54 55 -- 12.75                                                                            45 --                                      PET, 45,000         -- -- -- 55 -- -- 45                                      Impact modifier: SEBS, %                                                                          10 10 9  9  10.1                                                                             10 10                                      Izod impact strength (notched), joules/m.                                                         753                                                                              134                                                                              219                                                                              64 630                                                                              625                                                                              673                                     Tensile strength at yield                                                                         4.39                                                                             4.75                                                                             4.90                                                                             5.31                                                                             4.78                                                                             4.39                                                                             --                                      Tensile strength at break                                                                         4.09                                                                             4.16                                                                             4.34                                                                             4.83                                                                             4.57                                                                             4.41                                                                             --                                      Elongation at break, %                                                                            130                                                                              70 38 75 77 81 --                                      Tensile modulus     77.2                                                                             -- -- 80.0                                                                             56.2                                                                             37.6                                                                             --                                      Heat distortion temp., °C.                                                                 161                                                                              167                                                                              -- -- -- -- --                                      __________________________________________________________________________

What is claimed is:
 1. A composition comprising copolymers havingpolyphenylene ether moieties comprising a plurality of structural unitshaving the formula ##STR10## wherein in each of said unitsindependently, each Q¹ is independently halogen, primary or secondarylower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, orhalohydrocarbonoxy wherein at least two carbon atoms separate thehalogen and oxygen atoms; and each Q² is independently hydrogen,halogen,. primary, or secondary lower alkyl, phenyl, haloalkyl,hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹ ; connected topoly(alkylene dicarboxylate) moieties containing at least 30 alkylenedicarboxylate units by polyvalent linking groups containing one or morecarboxamide groups.
 2. A composition according to claim 1 wherein thepoly(alkylene dicarboxylate) moieties comprise at least 50 structuralunits of the formula ##STR11## wherein R³ is a divalent aliphatic oralicyclic radical containing about 2-10 carbon atoms and R⁴ is adivalent aliphatic, alicyclic or aromatic radical containing about 2-10carbon atoms.
 3. A composition according to claim 2 wherein the linkinggroups have a formula weight up to about
 1500. 4. A compositionaccording to claim 3 wherein the polyphenylene ether is apoly(2,6-dimethyl-1,4-phenylene ether).
 5. A composition according toclaim 4 wherein the polyester is a poly(ethylene terephthalate) or apoly(1,4-butylene terephthalate).
 6. A composition according to claim 5wherein the polyester is a poly(1,4-butylene terephthalate).
 7. Acomposition comprising copolymers having the formula

    A--Z.sup.1 --B                                             (I)

wherein A is derived from a polyphenylene ether comprising a pluralityof structural units having the formula ##STR12## and in each of saidunits independently, each Q¹ is independently halogen, primary orsecondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, orhalohydrocarbonoxy wherein at least two carbon atoms separate thehalogen and oxygen atoms; and each Q² is independently hydrogen,halogen, primary or secondary lower alkyl, phenyl, haloalkyl,hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹ ; B is apoly(alkylene dicarboxylate) moiety and Z¹ is a divalent linking groupcontaining one or more carboxamide groups.
 8. A resinous compositioncomprising a poly(alkylene dicarboxylate); an epoxy-functionalizedpolyphenylene ether prepared by reacting a polyphenylene ether with atleast one of glycidyl methacrylate, glycidyl acrylate, glycidyl ethylmaleate, glycidyl ethyl fumarate and allyl glycidyl ether; and anyreaction products thereof.
 9. A composition according to claim 8 whereinthe polyphenylene ether comprises a plurality of structural units havingthe formula ##STR13## and in each of said units independently, each Q¹is independently halogen, primary or secondary lower alkyl, phenyl,haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy wherein atleast two carbon atoms separate the halogen and oxygen atoms; and eachQ² is independently hydrogen, halogen, primary or secondary lower alkyl,phenyl, haloalkyl, hydrocarbonoxy or halohydrocarbonoxy as defined forQ¹.
 10. A composition according to claim 9 wherein the polyphenyleneether is a poly(2,6-dimethyl-1,4-phenylene ether).
 11. A resinouscomposition comprising a poly(alkylene dicarboxylate); anepoxy-functionalized polyphenylene ether prepared by reacting apolyphenylene ether with terephthaloyl chloride and subsequently withglycidol; and any reaction products thereof.
 12. A composition accordingto claim 11 wherein the polyphenylene ether comprises a plurality ofstructural units having the formula ##STR14## and in each of said unitsindependently, each Q¹ is independently halogen, primary or secondarylower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, orhalohydrocarbonoxy wherein at least two carbon atoms separate thehalogen and oxygen atoms; and each Q² is independently hydrogen,halogen, primary or secondary lower alkyl, phenyl, haloalkyl,hydrocarbonoxy or halohydrocarbonoxy as defined for Q¹.
 13. Acomposition according to claim 12 wherein the polyphenylene ether is apoly(2,6-dimethyl-1,4-phenylene ether).